Prepared resin



Patented May 5, I936 UNITED STATES PATENT OFFICE PREPARED RESIN OharlesA. Thomas, Dayton, Ohio, assignor to Monsanto Petroleum Chemicals,1110., Dayton, hio,'a corporation of Delaware No Drawing. Originalapplication November 10, 1930, Serial No. 494,692. Divided and thisapplication'July 15, 1935, Serial No. 31,440

24 Claims. (Cl. 260-2) This invention relates to the manufacture of andxylene in substantially equal proportions by artificial or preparedresins, and coating mateweight of each of the named reactiveconstiturials produced from prepared resins: the present ents.

application is a division of.my'co-pending aph e a p given above lireillustrative 0f 5 'plication, Serial Number 494,692, filed Novemberproportions of the reactive materials which may 5 10, 1930. be used.However, the proportions of such re- One of the principal objects ofthis invention active materials used in carrying out this procis toprovide such a prepared resin having unless may be varied widely ep ndino h perusual and valuable reactive and combining powticular qualitiesdesired in the es n to be p 1() er, and amethod of preparing h a, resinduced. Resins are produced by reacting mixtures Another object is toprepare such a prepared of the above described materials insubstantially resin, by reacting a. synthetic resin with other ll poporti n Th m l r p por n f materials to produce a resultant resinreaction a dioleflne and an'olefine, or a, diolefine and a producthaving superiop har t ri ti substituted benzene, or a, diolefine and'anolefine Another object is to rovide a protective coatand a u s ubenzene, a been f und to 15 ing material made from such prepared resin,p u e resins Ve y Sat cto y for many uses.- which coating materialproduces a very flexible T pr p ns best p to pr duce h and substantiallywater-proof film. properties desired in the resulting resin, and atOther objects and advantages of the invention e ame time produce a yieldf resin large will be apparent from the following description n h r mi ap d an eadily and appended claims. be determined by experiment; It hasbeen found In the practicing of this invention a synthetic that anincreased Dr0p0rti0n 0f Olefine p odu e resin is first produced byreacting a. diolefine a softer resin, and where a hard resin is desired.

, such as i o r w th a olefine h as amylene; it is not desirable to havethe amount of olefine or by reacting a diolefine, such as isoprene, withx d the am unt f d o fin C ns qu n l a, substituted benzene such as analkyl benzene, where .a ft resin is desired, the olefine content such astoluene, or the xylenes and their homoshould be increased. In reacting adioleflne with logues; or by reacting a mixture of unsaturatedSubstituted benzene, t a ee found that the hydrocarbons such'as arepresent in. certain i'raciodine number of the resulting resin pp s to 30tions of cracked distillate. These materials are increase decrease indirect ratio to the p reacted or polymerized in'the presence of asuitportion o iplefine used. Thus an increase in able catalyst, such aaluminu hlorid In the proportion of substituted benzene inreactproducing this resin various diolefines may be ving materialsconsisting o 8 xture of dioleused with various oleflnes or with varioussubfi and Substituted benzene, pp a to p oduce stituted benzenes, in themanner described in a sin havin a smaller iodine number. 35 theco-pending applications of 4 Charles A. It has also been found that whena substituted Thomas and Carroll A. Hochwalt, Serial Number benzene hasbeen used as one of the reacting ma- 294,491, Patent Number 1,836,629,filed July 21, e lal the resulting unsaturated hydrocarbon 1928, a d ofCharle A Thomas, Serial Numb r resin is particularly reactive andcombines read- 40 461,807, filed June 17, 1930, and of Charles A. ilywith o h r m i l op n reaction pr d- 40 Thomas, Serial Number 482,157,Patent Number ucts having distinctive and valuable properties.1,947,626, filed September 15, 1930. However, when a p oportion ofsubstituted ben- A atlSjactory synthetic r i h al b zene in excess ofmolecular proportions is used, produced by reacting together adiolefine, an olesuch excess appears to serve as a solvent rather fine,and a substituted benzene, or a mixture of than to enter into thereaction. In such case, a 45 unsaturated hydrocarbonscontaining thesethree resin is produced which is lighter in color than reactivesubstances, such as the fraction of, when the substituted benzene isused in moleccracked distillate distilled between 30 C. and ularproportions or less. 160 C; Thus a satisfactory resin has been pro-Various olefines and diolefines or mixtures 01' duced by reactingtogether isoprene, amylene these may be used in preparing this resin,for 50 and toluene in the proportions of approximately example, suchdiolefines as hexadiene, isoprene, 50 parts of isoprene and 50 parts ofamylene to and butadiene, and dimethyl bu -diene, may be 38 parts oitoluene. A somewhat similar resin, mentioned as representative membersof the having substantially the same acid number, was group. Asrepresentative oleflneswhich react 5 produced by reacting togetherisoprene, amylene, with dioleflne compounds in the manner described, maybe mentioned the amylenes, including-symmetrical and unsymmetricalmethyl ethyl ethylene, trimethyl eth'yl ethylene and normal propylethylene, or pentene-2. Other unsaturated hydrocarbons having one doublebond, or oleflnes, will react in this manner.

Various substituted benzenes may also be used with various diolefines orwith mixtures of diolefines and olefines. Satisfactory resins have beenobtained by this process using substituted benzenes such as toluene, orthe xylenes and their homologues. Other substituted benzenes may beused, such as cymene, ethyl benzene, diethyl benzene, normal-propylbenzene and isopropyl benzene, tetra-methyl benzene, secondary butylbenzene, tertiary butyl benzene, amyl benzene, tertiary amyl benzene,hexa-methyl benzene, hexa-ethyl benzene, or styrene (vinyl benzene).

Inasmuch as the resins described above are produced from unsaturatedhydrocarbons, they are termed herein for purposes of descriptionunsaturated hydrocarbon resins; but it is to be understood that suchdesignation does not refer to the chemical composition of the resinousproducts themselves but rather to the starting materials from which theresins are prepared.

Whatever reactive materials or mixtures of reactive materials arereacted to produce the un saturated hydrocarbon resin used in carryingout this invention, the same method may be followed. As an example ofthe method of producing an unsaturated hydrocarbon resin which has beeneffectively used in carrying out this invention the following procedureis described, using a mixture of unsaturated hydrocarbons included inthe fraction of cracked distillate distilled between 30 C. and 160 C. Itis to be understood that the term unsaturated hydrocarbons as usedherein, refers to hydrocarbon compounds which unite with othercompounds, such for example, as the halogens, to form addition productswithout splitting off a new compound. Unsaturated hydrocarbon compoundsare capable of giving the Baeyer test for unsaturation. (Text book ofOrganic Chemistry, Hoileman, 6th Edition, page 131.)

Mixtures containing unsaturated hydrocarbons which are eminently suitedfor the practice of this invention can be obtained by observing thefollowing conditions of cracking. As hydrocarbon charge stock, propane,butane, natural gas and other hydrocarbon gases, naphtha, gas oil,kerosene and other liquid hydrocarbons can be used. Kerosene isespecially suitable as a charging hydrocarbon stock, particularly when'mixed with previously charged stock and with the hydrocarbon mixtureresulting from the resin production step, that is, the unconvertedportion of the mixture remaining after resinformation subsequent to thetreatment of the cracked distillate with metallic halides and theremoval of the latter catalysts. The cracking temperature is maintainedpreferably at above 900 C. and the time of contact of the gases at from0.1 to 0.2 seconds although a wide range of temperatures givessatisfactory cracked dis tillates when the time of contact is suitablyadjusted.

A stock consisting of 90 parts by volume of commercial kerosene and 10parts by volume of an aromatic hydrocarbon mixture consisting of 50parts by volume of benzene, 30 parts of toluene and 20 parts of xylenes,is charged at the rate of 0.53 gallons per hour through a 12.5 feetNichrome V tube, having an internal diameter of one-quarter inch, heatedat 875 C. Nichrome alloys have been found particularly suitable for thispyrolytic operation, although it is to be understood that the pyrolysismay be conducted in contact with other materials of construction eventhough their effectiveness from a mechanical standpoint under theextreme conditions of pyrolysis may leave something to be desired. Steamis added in small quantities (usually one per cent by volume or more)continuously to prevent obstruction of the tube by deposited carbon. Theissuing gases are condensed and the condensate which collects amounts to59% by weight of the charged stock whereas the uncondensed gas amountsto 41% by weight of thecharged stock. The off gas has a volumecomposition corresponding to 0.1% carbon dioxide, 1.8% carbon monoxide,18.4% hydrogen, 30.9% methane, 34.4% ethylene, 3.9% ethane, 0.2%acetylene, 7.3% propylene, 1.6% butylenes and 1.4% pentanes and higherhydrocarbons. Of the liquid condensate, 30% by Weight is tar having aboiling point above approximately 300 C., 6.5% are heavy oils unsuitedfor conversion to resin and boiling about 260 C., and the remainder,boiling below about 260 C., is condensate suitable for conversion toresin. The use of steam in the recovery by distillation of the desiredfraction is useful to retard premature polymerization and gum formation.

This mixture is placed within a suitable container or polymerizingvessel, and an activating compound such as powdered anhydrous aluminumchloride (A1013) is added while the mixture in the vessel is beingagitated. The aluminum chloride is preferably pulverized to give bettercontact, and is added in small quantities at a time while the contentsof the polymerizing vessel are being agitated. For example, presumingthat 25 gallons of a mixture of active ingredients are to be treatedwithin the polymerizing vessel, aluminum chloride may be added inquantities of approximately 6 to 8 ounces at a time. With the additionof the first batch of aluminum chloride, there is a rather activechemical reaction with a resultant rise in temperature. It is desirableto contol the temperature of the reaction inasmuch as this has a bearingupon the character of the resultant resin, particularly the hardnessthereof. The reaction is preferably carried out above 20 C., as then theresultant resin is very materially harder and the yield is somewhatgreater than when the reaction is carried out below 20 C. However, it isdesirable where an atmospheric polymerizing vessel is used that thetemperature should not be permitted to rise much above 40 C. Otherwisethe polymerizing vessel should be kept under pressure to prevent unduevolatilization and loss of resin. Polymerization at higher temperatures,such as above C., requires a special pressure vessel. Very satisfactoryresults are secured when the temperature is controlled between 25 and 35C., this being readily accomplished by introducing the aluminum chloridein small amounts with proper agitation to prevent local overheating andby cooling the reaction mass by a suitable cooling jacket. Thispolymerizing reaction is preferably carried out in the absence of water.Water present during the reaction hydrolyzes the catalyst to form anacid which in turn aifects butanes and.

the reaction, resulting in a darker and quite different resin product.

. production. In any event, it is desirable Additional batches ofaluminum chloride are added from time to time as may be done withoutunduly increasing the temperature of the reaction mass, and this isrepeated with continuous agitation until no further temperatureriseresults. The amount of aluminum chloride used is also controlled inaccordance with the materials being treated, as this is found to have abearing upon the yield. It is found that the larger the volume of activeingredients being treated at any one time, the lesserthe amount ofcatalyst needed per unit weight of active ingredients for optimumresults. Thus when treating the above mixture in twenty-five gallonbatches, very satisfactory results are secured by the addition of aboutthree pounds of catalyst, this being equivalent to approximately 1.4grams of catalyst for 100 cc. of active ingredients. Where smallerbatches are being treated, such for ex- I ample as abatch of 100- cc. anincreased proportion of catalyst is used to give maximum yield,generally about 3.5 to 3.7 grams of aluminum chloride per 100 cc. ofactive ingredients giving optimum results. The quantity of catalystneeded for best results can be readily determined by tests for theparticular ingredients being treated, so that this amount can be used inregular plant that the amount of catalyst used be not increasedmaterially over four gramsper 100 cc. of active ingredients, as thecharacter of the resultant resin may be deleteriously influenced.

In addition to aluminum chloride, other compounds which hydrolyze inwater giving an acid reaction will function satisfactorily to cause theconversion of the active ingredients into resin,-- for example chloridesof iron, boron, zinc, antimony, indium, titanium and tin. The time ofthe treatment is also found to have a bearing upon the resultant resin,particularly the color. The reaction may proceed as much as 12 hours,but it is found desirable not to leave the-catalyst in contact with thematerials for a period of time much in excess of this, as the resin maybe darkened. The reaction is preferably completed in less time, such asabout 6 to 8 hours, this giving optimum results. I

It has been found that the end of the polymerization reaction isindicated when the mixture has reached a constant density. This point isconveniently determined by making density determinations on samples ofthe polymerized mixture at half hour periods when the polymerizationreaction is nearing completion. When the density is found to be constantat three succes-.

sive periods, the polymerization reaction will usually be found to becomplete. The reaction time for plant use may be readily determined inthis manner on a trial, run for specified materials and amounts.v

The resulting reaction product is a viscous mass dark in color. Thisviscous material is then neutralized to terminate or kill thepolymerizirg reaction. Various water soluble alkalies may be used forthis neutralizing, but preferably ammonia'is employed as the excess ofthis material can be removed by distillation and has no injuriouseffects on the resulting resin. The neutralizing treatment is preferablycarried out in the presence of an organic hydroxy compound, which iseffective to-supply hydroxyl radicals for the decomposition andprecipitation of the aluminum chloride or other activating agentpresent. An alcohol, such as ethyl alcohol, functions-verysatisfactorily for this purpose. Thus a mixture 80 C., or until the ofabout 40% by volume of ammonium hydroxide containing 28% NI-Ia by weightand 60% by vo ume of 95% ethyl alcohol gives good results. With thequantities specified above, slightly more than 3 gallons of this mixtureis used,- the amount theoretically required being approximately oneabovemixture. The mass is agitated constantly during the neutralization and agranular precipitate of the activating agent is .produced which isreadily removed by filtration for example where aluminum chloride isused a precipitate of aluminum hydroxide and ammonium chloride isformed. The neutralization is accompanied by a color change, thereacting mass changing from a black or dark red to a yellowish red oryellow as the neutralization is completed. The neutralizing reaction iscompleted in about a half hour.

After the neutralizing reaction is completed the contents of theneutralizing vessel are preferably a heated by means of a suitabletemperature con trolling jacket to a temperature of about 60 C.-

distillate comes over clear. That is, the distillation is continued tillno more water comes over. For the amounts specified, this operationis-continued 1-2 hours. During this heating substantially all the excessammonia and alcohol is liberated and is allowed to pass off to asuitable condenser for the recovery of the distillate. From thedistillate, ammonia and alcohol may beseparated and recovered. In thisprocess 'it is found desirable that substantially all of the water andNH: be removed to prevent precipitation of the resin and consequentclogging of the filter.

When the neutralization is carried out in the presence of water asdescribed above, the subsequent distillation is more difficult and watermay be occludedinthe resin resulting in an opaque product. Where a,clear resin is essential, or for more convenient plant operation, it maybe desirable to carry out the neutralizing operation in the absence ofwater. In such case an anhydrous alcohol or other organic hydroxy liquidsaturated with dry NH3 gas can be used for the neutralization with verysatisfactory results. When no aqueous solutions have been used, theabove distillation can be carried out in less time than specified above.

When reacting the mixture of unsaturated hydrocarbons in this manner, itis found thattwo products are formed, one being an amorphous resincompound readily soluble in benzol, and another being such solvent. Thisinsoluble compound is carried'down in the precipitate. In order toinsure complete solution of the resinous product and to facilitate thefiltering operation, an organic solvent which is immiscible with water,such as benzol, is added to the neutralized mass after free water andammonia have been distilled off. In the distillation processapproximately onehalf the volume of the original reaction mixture may bedistilled off. i The amount of solvent added is then approximately equalto the volum distilled off; that is, for the quantities specified aboutI! gallons of benzol are added to the neutralized and distilled mass.

The neutralized mass mixed with benzol is then passed through a suitablefilter,- such as a conventional filter press, where the undissolvedmaterials including the precipitatedactivating agent are removed fromthe liquid. The filtered treated to recover aluminum-goxide (Al-203) anda gelatinous compound insoluble in ammonium chloride (NHrCl) asby-products. In place of the filter press a suitable type of centrifugemay be used if desired.

The clear filtrate containing the resin in solution is allowed .to passinto a distillation vessel provided with a suitable heating jacket forthe introduction of a heating medium such as steam or oil. The materialwithin the distillation vessel is now heated to distill off the morevolatile constituents; including benzol and any remaining alcohol, whichmay pass off to a suitable condenser so as to be recovered for repeateduse in the process. Distillation is continued until a thermometer in thedistillation line rises to approximately C., at which time substantiallyall of the benzol and any remaining small amounts of alcohol and water,will have been driven off of the resulting resin which is left in thedistillation vessel as semi-fluid or pasty mass, termed herein a "softresin. This soft resn contains varying proportions of higher oils,primarily unsaturated hydrocarbon oils of rather high molecular weightand perhaps some unreacted substituted benzene, which are not removed bydistillation at temperatures not exceeding 100 C. If a solid or hardresin is desired, the distillation is continued as described above untilsubstantially all of the readily volatile solvents and higher oils havebeen driven off.

If hard resin, free from the higher oils is desired, the resin may beagain placed in a hydrocarbon solvent such as benzol and reprecipitatedby alcohol or acetone, the higher oils remaining in solution in thebenzol and alcohol mixture. This solution mixture may be separated bydecanting the two formed layers, and the precipitate may then be heatedunder vacuum which drives off all alcohol and benzol, and a clearbrittle resin results.

It has been found that where a gas such as steam, carbon dioxide, air,oxygen or the like is passed through the resinous mass, and kept wellagitated, the heating jacket may be raised to a higher temperature ofthe order of C. with a resultant rapid increase of the drying andhardening of the resin without injury to the resin. This may be readilyaccomplished by supplying oil heated to a temperature of about 180 C. tothe external jacket, while a gas is being passed into the well agitatedresinous mass. This treatment drives off the remaining solvent andhigher oils present in the resin which tend to make it soft. Whensubstantially pure materials are used, this hardening process ismaterially shortened, due to the fact that the higher oils which tend tomake the resin soft are largely formed from impurities present in thestarting materials. When it is desired to produce a hard resin having asubstant ally neutral reaction, a non-oxidizing gas, such as carbondioxide, may be passed through the heated resinous mass.

By avoiding the use of steam or substantial quantities of waterthroughout the drying process, the occlusion of water in the resin isavoided and a clear product obtained. But steam distillation may be usedif the occluded H2O makes no difference in the product, that is, when aclear resin is not des red. Means may be used to free this occluded H2Ofrom the hardened resin, when it is desired to use a steam distillationin hardening the resin.

The unsaturated hydrocarbon resin produced in this manner is hard. lightin color. and clear when the occlusion of water has been avoided, asabove described.

a reaction product The unsaturated hydrocarbon resins produced in thismanner have, as a general rule, higher iodine values than otherhydrocarbon resins, some of these resins having an iodine number above75 and as high as 200. This property appears to be indicative of certainvaluable characteristics of the resin. For example, it has been foundthat the reactivity of the resin is in many cases proportional to theiodine number of the resin; that is, a resin having a higher iodinenumber is usually more reactive than a resin made from startingmaterials of the same type and having a lower iodine number. Theunsaturated hydrocarbon resin is soluble in petroleum hydrocarbonsolvents and is suitable for making coating materials, molding compoundsand for other useful purposes. When this resin, in solution in asuitable paint or varnish solvent, such as mineral spirits, 'is used asa coating material, a film is produced which dries rapidly, is unusuallydurable, and is substantially waterproof. This film, however, becomessomewhat brittle on drying and does not have the extraordinaryflexibility required foncertain types of protective coating. Thedescribed resin also combines readily with the usual drying oils to makeprotective coating materials. The product produced by combination withdrying oils is superior in certain respects to most coating materials,and the film formed therefrom is superior in certain characteristics,particularly flexibility, to the film formed from the resin alone in apaint or varnish solvent. It has also been found that an excellentcoating material can be produced by heating a mixture of the describedunsaturated hydrocarbon resin with a drying oil and a nondryingvegetable oil, such as castor oil. The preparation and properties of theabove mentioned coating materials are more fully described and claimedin the co-pending applications of Charles A. Thomas and Carroll A.Hochwalt, Serial Number 470,534, filed July 24, 1930, and of Charles A.Thomas and Carroll A. Hochwalt, Serial Number 470,535, filed July 24,1930.

It has also been found that this described unsaturated hydrocarbon resinhas the unusual property, when heated with a non-drying oil, such ascastor oil, of reacting with such oil alone to form a new resinousreaction product. Such a reaction product may be made from widelyvarying proportions of castor oil and resin, the hardness of the productvarying with the proportion of oil used. By way of example, when castoroil, which is composed essentially of a glyceride of ricinoleic acid andthe described unsaturated hydrocarbon resin in about equal proportionsby weight, are heated together at about 310 C. for about two hours, themixture reacts to form a new resinous product. The occurrence of achemical reaction during the heating of the mixture, is indicated byfoaming, and the formation and giving off of water as a product of thereaction. The resulting product is also found to have a lower iodinenumber than the original resin. This reaction product upon cooling,forms a hard resin, soluble in varnish solvents. When a solution of thisresin product in a varnish solvent, such as mineral spirits, is brushedon a surface, it dries to form a usable film which is waterproof andquite flexible. The formation of such is novel, and one not to beexpected, since other known synthetic resins do not react with castoroil, and will not produce with castor oil a product which dries to forma usable film. The film produced from the reactlon product of thedescribedlresin with castor oil is water-proof and is more flexible thanthe film produced fromthe product of the resin with the usual ying oils.It is also more flexible than the film produced from the product of theresin with a mixture of drying oil and non-drying oil.

It has further scribed unsaturated ,hydrocarbon appears to react withpolyhydric alcohols such as ethylene glycol, glycerin and the like, toform a new product. For example, when the described unsaturatedhydrocarbon resin in mixed with glycerin in the proportions of about 5to 40% by weight of glycerin, based on the weight of the resin, and themixture heated to a reacting temperature, for example about 280 0.,a'deflnite reaction appears to take place. The mixture foams and anappreciable amount of water is given oil which may be collected. Whenthe resulting reaction prodnot is allowed to cool, it isfound to be ahard resin h inal resin; When dissolved in a varnish solvent such asmineral spirits, and brushed on a surface, the resin forms afilm whichdoes not have the high degree of flexibility required in certain coatingmaterials.

It has been further discovered that the described unsaturatedhydrocarbon resin may also a be reacted with a combination of avegetable oil such as castor oil, and a polyhydric alcohol such asglycerin, to produce a still difierent resinous reaction product, whichis very superior, particularly as to flexibility of the film producedtherefrom.

It has been found that on heating castor oil alone, a saponificationreaction takes place, setting free the castor oil acids. In order toprevent such separation, castor may be heated with a polyhydric alcohol,such as glycerin, and the reesterified product heated with the describedunsaturated hydrocarbon resin to form a new resinous product.

The reaction mixture consisting of the reesterified castor oil, and thedescribed unsaturated hydrocarbon resin may be subjected to furtherheating with an additional amount of a polyhydric alcohol, such asglycerin. A reaction product may also be produced by heating together amixture of a po yhydrlc alcohol, castor oil, and the describedunsaturated hydrocarbon resin, but a reaction product so formed is foundto have somewhat different properties. Various polyhydric alcohols, suchas glycerin, ethylene glycol,

and the like, are suitable for carrying on this reaction.

As an example of the production of this new resinous reaction product,the following procedure is described. The reaction is preferably carriedon in vessel made from or lined with material not a ected by thereaction. Glass or aluminum vessels have been found satisfactory, and

it has usually been found that the use of iron vessels appears toproduce a darker colored product. The vessel is also provided with asuitable condenser so that water and other volatile products of thereaction which distil over during the heating processes are removed fromthe reaction mass, and may be collected. If desired, the material may beagitated throughout the process or at any part thereof, by any suitablemechanical means. 100 parts by weight of blown castor oil are heated ina suitable vessel, such as described, to about 310 C., oruntil the massbegins to jell or polymerize. The polymerization reaction which takesplace during the heating is not enbeen discovered that the deaving alower iodine number than the origto about 285 soluble in chloroform.

naphtha and the like.

"degree. After such a softened by lacque tirely understood, butapparently water is split 0! during the reaction. When the reaction hasreached the desired point, as indicated when the material jells, themass is allowed to cool to about 260 0. About 6 parts by weight ofglycerin are then added. The mixture is then heated to about 285 (2., oruntil it begins to thin somewhat. When the mixture has reached a thin oroily consistency, 100' parts by weight of the unsaturated hydrocarbonresin herein before described are added. The exact time at which theresin is to be added must be judged by experiment, and by constanttesting of the material so that the point when it begins to thin may bedetermined. After the addition of the resin, the temperature of themixture will be somewhat below 285 0., generally between 260 and 285 C.,and the reaction mass is held at, that temperature until it appearsclean-that is, until a sample dropped on a metal plate, according to theusual practice of varnish makers in testing varnish materials, gives aclear pill, or drop of material. This heating may require about 1 hour.The mixture is then cooled to about 260 0., and about 3 parts by weightof glycerin are added. The mixture is again heated to about 310 C. andheld at that temperature until .bodying\begins,that is, until themixture begins to thicken. The proper degree of bodying isdetermined byexperiment. This may be done by the usual methods employed by varnishmakers, and is somewhat dependent on the consistency desired forparticular uses. When the desired body has been reached, the mixture iscooled 0., and at this temperature the desired amount of mineral spiritsor other varnish thinner is added, in order to produce a material whichwhen cooled will be of the desired consistency for use as a coatingmaterial. During the whole process above described, the volatileconstituents are being distilled oil, and may be collected and weighedif desired, so that the total weight of the remaining product may becalculated and considered in relation to the amount of thinner to beadded. The thinner is preferably added as described at the temperatureindicated, because the reaction product dissolves more slowly when cold.On cooling after addition 01' the thinner, the material isready for useas a coating material.

The resinous reaction product thus produced, when allowed to hardenwithout solution in a solvent, has the general appearance of syntheticrubber. It is tough and does not become hard at ordinary temperatures.This resinous product is benzol, alcohol, and varnish solvents, such asWhen dissolved in a varnish solvent, such as solvent naphtha or mineralspirits, a clear solution is formed. When brushed on a surface, thissolution leaves a clear yellowish film which dries quickly without theuse of a metallic dryer. Films made from this material were subjected toan accelerated aging test by baking at 120 C. for various periods oftime. Under such treatment the film stands up remarkably well, andretains its flexibility to a most unusual film on a metal sheet had beensubjected to the baking process described for as long as 200 hours, themetal sheet could be bent double several times in. succession withoutcracking, or injuring the film. The described film is also substantiallywater-proof, and very resistant to acids and alkalies, its durabilitybeing very satisfactory. Due to the fact that this film is not it isparticularly suitable for use as an under-coat or prime coat for othercoating material. The material is also adapted for use with pigments inthe usual manner to make coating materials. Because of its greatflexibility and durability the material is of special value for use onsurfaces subject to shock or strain. This resinous material is alsoadapted for use as a molding compound, with or without pigments, fillingmaterial and the like.

Reaction products have also been produced by reacting the describedunsaturated hydrocarbon resin with various esterified fatty acids ofvegetable oils, according to the process described above. For example,the commercial fatty acids of linseed oil or a mixture of commercialfatty acids of linseed oil and commercial fatty acids of china wood oil,may be esterified by reaction with glycerin, and the esterified productsreacted with the unsaturated hydrocarbon resin and an additional amountof glycerin, according to the process described, and using the sameproportions indicated in the example given. The resulting resinousproducts when dissolved in a varnish solvent, and brushed on a surface,dry to form films which are quite flexible, but become brittle afterbaking at 120 C. for 18 hours. These films are not waterproof.

When commercial castor oil acids are reacted with glycerin, and theesterified product reacted with the unsaturated hydrocarbon resin and anadditional amount of glycerin, according to the process described above,using the same proportions indicated in the example given, a resinousreaction product is also obtained. This resinous product when dissolvedin a varnish solvent and brushed on a surface, dries to form a filmwhich is flexible, but which becomes brittle after baking for 18 hoursat 120 C. This film is also not entirely water-proof.

While the methods and processes herein described and the products soproduced constitute preferred embodiments of this invention, it is to beunderstood that the invention is notlimited to these precise methods orprocesses, or precise products, and that changes may bemade thereinwithout departing from the scope of the invention which is defined inthe appended claims.

What I claim is:

1. The reaction product of a pre-formed synthetic hydrocarbon resin,obtained by the polymerization of a cracked petroleum distillate, withcastor oil, unmixed with a drying oil.

2. The reaction product of castor oil, unmixed with a. drying oil, and apreformed hydrocarbon resin formed by polymerization of an olefine and adiolefine, such reaction product on solution in a varnish solvent beingcapable of drying in film form so as to form a usable protectivecoating.

3; The method in the preparation of a resinous reaction product adaptedfor use in coating materials, which comprises heating a glyceride ofricinoleic acid to a reaction temperature with a preformed unsaturatedhydrocarbon resin obtained by polymerization of an olefine and adiolefine, to produce a resinous reaction product which in solution in asolvent is capable of drying to a usable film.

4. The reaction product of a pre-formed synthetic hydrocarbon resinobtained by the polymerization of a cracked petroleum distillate withcastor oil'unmixed with a drying oil.

5. The method in the preparation of a resin- 'ous reaction product whichcomprises heating a pre-formed synthetic unsaturated hydrocarbon resinobtained by the polymerization of a cracked ous reaction petroleumdistillate with a glyceride of ricinoleic acid to a reactiontemperature.

6. The reaction product of castor oil unmixed with a drying oil and apre-formed, ethyl alcoholinsoluble, unsaturated hydrocarbon resin formedby the polymerization of a diolefine and at least one other unsaturatedhydrocarbon.

'7. The reaction product of castor oil and a substantially neutralunsaturated hydrocarbon resin obtained by the polymerization of adiolefine with at least one of the following: olefines and alkylbenzene.

8. The product as defined in claim 7 and further characterized in thatthe polymerization is effected in the presence of a metallic halidepolymerizing agent.

9. The reaction product of castor oil and a substantially neutralhydrocarbon resin formed by the polymerization of a diolefine and atleast one of the following: an olefine and alkyl benzene; under theinfluence of a metallic halide polymerizing agent.

10. The method in the preparation of a synthetic resin which comprisesproducing an unsaturated hydrocarbon resin by polymerizing a mixture ofunsaturated hydrocarbons present in a cut of cracked petroleumdistillate in the presence of a metallic halide catalyst, separatelyheating castor oil with glycerin, and reacting such unsaturatedhydrocarbon resin with the reaction product of glycerin and castor oil.

11. The method in the preparation of a resinproduct which comprisesheating castor oil with a polyhydric alcohol, adding to the heatedmixture an unsaturated hydrocarbon resin, formed by polymerizing adiolefine and at least one other hydrocarbon, and continuing the heatingthereof, and then adding an additional quantity of polyhydric alcoholwhile continuing the heating of the reaction mass.

12. The reaction product of an unsaturated hydrocarbon resin obtained bythe polymerization of a cracked petroleum distillate with glycerin andcastor oil such reaction product in solution in varnish solvent beingcapable of drying in film form so as to form a usable protectivecoating.

13. The ethyl alcohol-soluble reaction product of an ethylalcohol-insoluble unsaturated hydrocarbon resin, obtained by thepolymerization of a cracked petroleum distillate, with glycerin andcastor oil, such reaction product in solution in a varnish solvent beingcapable of drying to a usable film without use of metallic driers.

14. The method in the preparation of a resinous reaction product adaptedfor use in coating materials, which comprises polymerizing a mixture ofcracked petroleum hydrocarbons in the presence of a metallic halidecatalyst to produce an unsaturated hydrocarbon resin, insoluble in ethylalcohol, separately heating castor oil with glycerin, and heating suchobtained reaction product of castor oil and glycerin with the preformedhydrocarbon resin to form a resinous reaction product soluble in ethylalcohol and capable of producing a waterproof film which is notmaterially softened by lacquer.

15. The method in the preparation of a synthetic resin adapted for usein coating materials, which comprises reacting by heat a mixture ofglycerin and castor oil, adding to the reaction mixture an ethylalcohol-insoluble unsaturated hydrocarbon resin, obtained by thepolymerization of a cracked petroleum distillate, heating to produce areaction between the hydrocarbon tion in a solvent; of drying to ausable film without use of metallic driers. Y

16. The method in the preparation of a resinous reaction product adaptedfor use in coating materials, which comprises heating castor oil with apolyhydric alcohol, adding to the heated mixture an ethylalcohol-insoluble substantially neutral unsaturated hydrocarbon resin,obtained by the polymerization of a cracked petroleum distillate;reacting the resulting mixture with heat, and then heating the resultingproduct with a polyhydric alcohol to produce a resinous reaction productsoluble in ethyl alcohol and in varnish and lacquer solvents, theresinous reactionproduct in solution in such solvent being capable ofdrying to a usable film without use of a metallic drier, to produce a,flexible waterproof film.

17. The reaction product of a synthetic hydrocarbon resin obtained bythe polymerization of a cracked petroleum distillate with the reactionproduct of a polyhydric alcohol and castor oil.

18. The method in the preparation of a synthetic resin which comprisesreacting by heat a mixture of glycerin and castor oil, adding to thereaction mixture a synthetic unsaturated hydrocarbon resin obtained bythe polymerization of a cracked petroleum distillate, and heating toproduce a reaction between the synthetic resin and the reaction mixture.

19. The ethyl alcohol-soluble reaction product of an ethylalcohol-insoluble unsaturated hydro carbon resin obtained by thepolymerizationof' (a cracked petroleum distillate, with a reactionproduct of a. polyhydric alcohol and castor oil.

20. The reaction product of a'polyhydric alcohol, castor oil and asubstantially neutral unsaturated hydrocarbon resiii formed by thepolymerization of a diolefine with at least one of the following: anolefine and an alkyl benzene.

21. The product as defined in claim 20 and further characterized in thatthe hydrocarbons are polymerized in the presence of a metallic halidepolymerizing agent.

22. The method of preparing a synthetic resin which comprises thermallyreacting a mixture of glycerin and castor oil, adding to the reactionmixture a substantially neutral unsaturated hydrocarbon resin obtainedby the polymerization of a diolefine with one of the following: anolefine and an alkyl benzene, and heating the resin and the reactedcastor oil and glycerin to reaction temperature.

23. The method as defined in claim 22 and further characterized in thatan additional quantity of a polyhydric alcohol is added during the laststage of heating. I

24. Thereaction product of glycerin, castor 'oil and a substantiallyneutral hydrocarbon resin obtained by the polymerization of a diolefinewith one of the following: an olefine and an alkyl benzene.

- CHARLES A. THOMAS.

